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PubMed2001

Capillary gel electrophoresis with sinusoidal voltammetric detection: a strategy to allow four-"color" DNA sequencing.

A novel detection strategy for DNA sequencing applications that utilizes a frequency-based electrochemical method is reported. Sinusoidal voltammetry is used to selectively identify four unique redox molecules that are covalently attached to the 5'-end of a 20-base sequencing primer. The tags used in this work are ferrocene derivatives with different substituents attached to the ferrocene ring, where the electron-donating or -withdrawing character of the substituent alters the half-wave potential of the modified ferrocene. Therefore, each tag has a unique SV frequency spectrum that can be easily identified in the frequency domain. In this work, the discrimination of one tag versus all others is accomplished through a "phase-nulling" technique. The signal for each tag is selectively eliminated while the other three responses remain virtually unchanged. This analysis scheme allows for the selective identification of each tagged oligonucleotide eluting in sieving polymer capillary gel electrophoresis with a separation efficiency of 2 x 10(6) theoretical plates per meter. This separation efficiency is sufficient to perform "low-resolution" DNA sequencing; the conditions used in this work have not yet been optimized for high-resolution sequencing applications.

DNA↗
PubMed2002

Electrochemical sensor for electrochemically inactive beta-D(+)-glucose using alpha-cyclodextrin template molecules.

We report an electrochemical sensor for an electrochemically inactive organic compound using a self-assembled monolayer (SAM) formed on the gold surface from a solution of thiolated alpha-cyclodextrin (alpha-CD). The SAM makes up an array of ultramicroelectrodes, which capture electroactive molecules such as those of ferrocene. When this SAM-modified electrode is exposed to a solution containing an electrochemically inactive compound, e.g., glucose, the captured ferrocene molecules are replaced by the electroinactive molecules via an equilibrium established between the two compounds, lowering the current for ferrocene oxidation. The decrease in current is directly proportional to the amount of glucose added and the glucose can be analyzed up to approximately 0.80 mM, which is approximately 1/10 of a typical physiological concentration in blood serum. Formation constants of the surface-bound alpha-CD molecules with ferrocene and glucose are also reported.

Binding, Competitive↗
PubMed2003

Microfabricated on-chip-type electrochemical flow immunoassay system for the detection of histamine released in whole blood samples.

This paper describes an on-chip-type electrochemical flow immunoassay system with a multichanneled matrix column. The multichanneled matrix column was functionally coated with cation-exchange resin and used for separation of proteins. Antihistamine immunoglobulin G (IgG) antibody conjugated with ferrocenemonocarboxylic acid (Fc) was also prepared and used as a novel analytical reagent. Antibody-antigen complexes were separated from free Fc-conjugated IgG antibody (Fc-IgG) on the basis of differences in isoelectric point (pI) using the multichanneled matrix column coated with cation-exchange resin. The assay yields a good relationship between current and histamine concentration in the range of 200-2000 ng/mL. This simple technique enables the assay of histamine released in whole blood within 2 min. Furthermore, a good correlation was found between the response of the electrochemical immunoassay described in this paper and the conventional RIA (radioimmunoassay). This on-chip-type electrochemical flow immunoassay requires only minute quantities of whole blood samples and generates highly reproducible results.

Electrochemistry↗
PubMed2003

Beta-cyclodextrin-based ferrocene-imprinted gold electrodes.

A new stepwise self-assembly procedure is described for the preparation of functional cyclodextrin-modified electrodes. The approach is based on the formation of alkanethiol/lipoylamide-beta-cyclodextrin monolayers with the thiol component responsible for blocking of the electrode surface and lipoylamide-beta-cyclodextrin molecules-for controlled opening of the access of the electroactive probe to the electrode. Functionalization of the electrode is achieved by means of a new cyclodextrin derivative-mono(6-deoxy-6-lipoylamide)-per-2,3,6-O-acetyl-beta-cyclodextrin-prepared in the peracetyl form and deacetylated directly on the electrode surface following the cyclodextrin self-assembly. The progress of deacetylation was monitored by the MALDI MS technique. Deacetylation caused opening of the active sites toward solution probes. The response toward ferrocene was found to be highly improved when ferrocene was added to the solution following self-assembly of cyclodextrin but prior to the thiol self-assembly step (imprinting method). The proposed synthesis and sequential monolayer formation scheme lead to well-organized and stable modified electrode surfaces with improved sensitivity toward solution species compared to other procedures of electrode modification with the cyclodextrin derivatives.

Algorithms↗
PubMed2003

Enzyme-amplified electrochemical detection of DNA using electrocatalysis of ferrocenyl-tethered dendrimer.

We have developed a sandwich-type enzyme-linked DNA sensor as a new electrochemical method to detect DNA hybridization. A partially ferrocenyl-tethered poly(amidoamine) dendrimer (Fc-D) was used as an electrocatalyst to enhance the electronic signals of DNA detection as well as a building block to immobilize capture probes. Fc-D was immobilized on a carboxylic acid-terminated self-assembled monolayer (SAM) by covalent coupling of unreacted amine in Fc-D to the acid. Thiolated capture probe was attached to the remaining amine groups of Fc-D on the SAM via a bifunctional linker. The target DNA was hybridized with the capture probe, and an extension in the DNA of the target was then hybridized with a biotinylated detection probe. Avidin-conjugated alkaline phosphatase was bound to the detection probe and allowed to generate the electroactive label, p-aminophenol, from p-aminophenyl phosphate enzymatically. p-Aminophenol diffuses into the Fc-D layer and is then electrocatalytically oxidized by the electronic mediation of the immobilized Fc-D, which leads to a great enhancement in signal. Consequently, the amount of hybridized target can be estimated using the intensity of electrocatalytic current. This DNA sensor exhibits a detection limit of 20 fmol. Our method was also successfully applied to the sequence-selective discrimination between perfectly matched and single-base mismatched target oligonucleotides.

Alkaline Phosphatase↗
PubMed2003

Amplified voltammetric detection of DNA hybridization via oxidation of ferrocene caps on gold nanoparticle/streptavidin conjugates.

Gold nanoparticle/streptavidin conjugates covered with 6-ferrocenylhexanethiol were attached onto a biotinylated DNA detection probe of a sandwich DNA complex. Due to the elasticity of the DNA strands, the ferrocene caps on gold nanoparticle/streptavidin conjugates are positioned in close proximity to the underlying electrode modified with a mixed DNA capture probe/hexanethiol self-assembled monolayer and can undergo reversible electron-transfer reactions. A detection level, down to 2.0 pM (10 amol for the 5 microL of sample needed) for oligodeoxynucleotide samples was obtained. The amplification of the voltammetric signals was attributed to the attachment of a large number of redox (ferrocene) markers per DNA duplex formed. The ferrocene oxidation current increased with the target concentration and began to level off at a target concentration of 10 nM. An Excellent linearity was found within the range between 6.9 and 150.0 pM and reasonable relative standard deviations (between 3.0 and 13.0%) were obtained. The amenability of this method to the analyses of polynucleotides (i.e., PCR products of the pre-S gene of hepatitis B virus in serum samples) was also demonstrated. The method is shown to be simple, selective, reproducible, and cost-effective and does not require labeling of the DNA targets.

DNA↗
PubMed2005

Simultaneously amplified electrochemical and surface plasmon optical detection of DNA hybridization based on ferrocene-streptavidin conjugates.

A sensitive method based on ferrocene-streptavidin (Fc-Stv) conjugates for the simultaneously amplified electrochemical and surface plasmon optical detection of DNA target hybridization to peptide nucleic acid-modified gold surfaces is reported. The attachment of Fc-Stv to the biotinylated complementary target DNA not only amplified the surface plasmon resonance signal but also enhanced the electrochemical signal due to the many Fc markers per Stv. The ferrocene redox peak current increased with the increase of the target DNA concentration. Consequently, the amount of hybridized target DNA can be estimated by cyclic voltammetry and chronocoulometry. The detection limit of this DNA sensor is 10 pM (2 fmol, with signal to noise > 3). This sensor was also shown to have high selectivity (at the single-base mismatch level) and good reproducibility.

DNA↗
PubMed2005

Separation of electron-transfer and coupled chemical reaction components of biocatalytic processes using Fourier transform ac voltammetry.

The underlying electron-transfer and coupled chemical processes associated with biologically important catalytic reactions can be resolved using a combination of Fourier transform ac voltammetry with an analysis of the separated dc and ac components. This outcome can be achieved because the response associated with generation of the catalytic current is essentially confined to the steady-state dc component, whereas the electron-transfer step is dominant in the fundamental and higher harmonics. For the mediated oxidation of glucose with glucose oxidase, it was found that the underlying reversible redox chemistry of the mediator, ferrocenemonocarboxylic acid, as detected in the third and higher harmonics, was totally unaffected by introduction of the catalytic process. In contrast, for the catalytic reduction of molecular oxygen by cytochrome P450, slight changes in the P450 redox process were detected when the catalytic reaction was present. Simulations of a simple catalytic reaction scheme support the fidelity of this novel FT ac voltammetric approach for examining mechanistic nuances of catalytic forms of electrochemical reaction schemes.

Catalysis↗
PubMed2005

Electrochemical method for the detection of lipase activity.

A novel electrochemical technique for the general assay of lipase activity is described. The method utilizes a solid-supported lipase substrate, which is formed by dripping and drying a small amount of an ethanol solution of 9-(5'-ferrocenylpentanoyloxy)nonyl disulfide (FPONDS) onto gold modified by a hexanethiol self-assembled monolayer. The redox ferrocene group of FPONDS generates the electrochemical signal, the intensity of which is proportional to the number of FPONDS molecules at the interface. Electrochemical and surface-enhanced infrared absorption spectroscopic data, as well as control experiments with an engineered, deactivated mutant enzyme, demonstrate that the wild-type lipase from Thermomyces lanuginosus is capable of cleaving the ester bonds of FPONDS molecules via an enzymatic hydrolysis mechanism, which includes the adsorption of the lipase onto the substrate surface. The hydrolysis liberates the ferrocene groups from the interface triggering a decay of the electrochemical redox signal. The rate of the electrochemical signal decrease is proportional to the lipase activity/concentration. These data suggest a general method for the direct measure of enzymatic activity of lipases.

Disulfides↗
PubMed2005

Electrochemical bioassay utilizing encapsulated electrochemical active microcrystal biolabels.

A new approach to perform electrochemical immunoassay based on the utilization of encapsulated microcrystal was developed. The microcrystal labels create a "supernova effect" upon exposure to a desired releasing agent. The microcrystal cores dissolve, and large amounts of signal-generating molecules diffuse across the capsule wall into the outer environment. Layer-by-Layer (LbL) technology was employed for the encapsulation of electrochemical signal-generating microcrystals (ferrocene microcrystals). The encapsulated microcrystals were conjugated with antibody molecules through the adsorption process. The biofunctionalized microcrystals were utilized as a probe for immunoassays. The microcrystal-based label system provided a high-signal molecule to antibody (S/P) ratio of 10(4)-10(5). Microcrystal biolabels with different antibody surface coverage (1.60-5.05 mg m(-2)) were subjected to a solid-phase immunoassay for the detection of mouse immunoglobulin G (M-IgG) molecules. The microcrystal-based immunoassay for the detection of M-IgG performed with microcrystals having antibody surface coverage of 5.05 mg m(-2) showed a sensitivity of 3.93 nA microg(-1) L(-1) with a detection limit of 2.82 microg L(-1).

Capsules↗
PubMed2005

Nanothin ferrocene film plasma polymerized over physisorbed glucose oxidase: high-throughput fabrication of bioelectronic devices without chemical modifications.

We describe a method for creating a mediator-containing interface between an enzyme and an electrode, achieving simpler and more reliable immobilization of the enzyme with the enhanced detection sensitivity. A nanothin polymer film containing a redox mediator, made of dimethylaminomethylferrocene, was plasma-deposited directly onto a glucose oxidase-physisorbed electrode, with which a relevant bioelectrochemical signal was observed without prior or further chemical modification of the enzyme molecules. The results of the surface characterizations before and after the enzyme immobilization showed that this method gave control over the spatial orientation of single enzyme molecules in favor of efficient and reproducible signal generation. Considering that the film deposition was performed using microfabrication-compatible organic plasma, our new method has a great potential of enabling high-throughput production of bioelectronic devices without chemical modification steps.

Adsorption↗
PubMed2005

Effect of electrolyte concentration on the viscosity and voltammetry of supercritical solutions.

The viscosity of a supercritical electrolyte solution is measured for the first time using a modified quartz crystal microbalance, and it is shown that ionic solvation leads to a significant structuring of the solvent and an appreciable increase in solution viscosity. Voltammetric investigations in the electrolyte solutions are used to confirm the magnitude of the viscosity changes, and these account for the appreciably lower than expected peak currents.

Borates↗
PubMed2006

Steady-state voltammetric response of the nanopore electrode.

The steady-state voltammetric response of the truncated conical-shaped glass nanopore electrode is presented. Analytical theory, finite-element simulations, and experimental measurement of the diffusive flux of a redox molecule through the pore orifice demonstrate that the steady-state current decreases rapidly as the pore depth increases and then asymptotically approaches a constant value when the pore depth is approximately 50x larger than the pore orifice. The asymptotic limit of the steady-state current is only a function of the pore orifice radius and the cone angle of the pore and has a finite value for all cone angles greater than zero. Experimental confirmation of the predicted dependence on pore depth is obtained using nanopore electrodes with 100-1000 nm orifice radii, by measuring the steady-state voltammetric current corresponding to the oxidation of ferrocene in acetonitrile solutions containing an excess of supporting electrolyte.

Computer Security↗
PubMed2006

Hybridization probe for femtomolar quantification of selected nucleic acid sequences on a disposable electrode.

Mixed monolayers of electroactive hybridization probes on gold surfaces of a disposable electrode were investigated as a technology for simple, sensitive, selective, and rapid gene identification. Hybridization to the ferrocene-labeled hairpin probes reproducibly diminished cyclic redox currents, presumably due to a displacement of the label from the electrode. Observed peak current densities were roughly 1000x greater than those observed in previous studies, such that results could easily be interpreted without the use of algorithms to correct for background polarization currents. Probes were sensitive to hybridization with a number of oligonucleotide sequences with varying homology, but target oligonucleotides could be distinguished from competing nontarget sequences based on unique "melting" profiles from the probe. Detection limits were demonstrated down to nearly 100 fM, which may be low enough to identify certain genetic conditions or infections without amplification. This technology has rich potential for use in field devices for gene identification as well as in gene microarrays.

Algorithms↗
PubMed2006

Label-free electrochemical detection of protein based on a ferrocene-bearing cationic polythiophene and aptamer.

Two label-free electrochemical methods for the detection of human alpha-thrombin using a water-soluble, ferrocene-functionalized polythiophene transducer and a single-stranded oligonucleotide aptamer probe are described. The first approach is a direct method in which the recorded current decreases upon addition of the targeted protein. The second one requires more steps and the additional utilization of PNA probes and nuclease enzyme. This indirect method leads to an increase of the electrical signal as a function of the concentration of human alpha-thrombin with a detection limit of 75 fmol.

Base Sequence↗
PubMed1998

Derivatization for electrospray ionization mass spectrometry. 3. Electrochemically ionizable derivatives.

In this paper, the use of ferrocene-based "electrochemically ionizable" derivatives to enhance ES-MS analysis of simple alcohols, sterols, and phenols is discussed. These derivatives are designed to take advantage of the electrolysis process inherent to operation of the ES ion source for selective ionization. Derivatization procedures, electrochemical character of the derivatives, and the ES-MS operational parameters necessary to maximize electrochemical ionization and to enhance gas-phase detection are presented with reference to ferrocenecarbamate ester derivatives of a variety of alcohol standards, as well as the ferroceneboronate derivative of the diol, pinacol. Tandem mass spectrometric analysis of the derivatives (precursor and product ion spectra) is shown to provide derivative confirmation, enhanced detection, and additional analyte structure information. The utility of this derivatization approach for the selective detection of alcohols in complicated mixtures is demonstrated using a saw palmetto (Serenoa repens) fruit extract known to contain a variety of alcohols at low levels.

Alcohols↗
PubMed2001

Cyclodextrin-based molecular machines.

Cyclodextrins have been used as a cyclic component in the construction of supramolecular architectures. Recently they have been studied as a component in the construction of rotaxanes and catenanes. A cyclodextrin ring can translocate in some rotaxane and catenane structures. Therefore, much attention has been given to cyclodextrins as a component of molecular shuttles, motors, and machines. Attempts to design and synthesize molecular-level machines using cyclodextrins as a cyclic component are described.

Cyclodextrins↗
PubMedDate not supplied

Synthesis of the first ferrocene-labeled dideoxynucleotide and its use for 3'-redox end-labeling of 5'-modified single-stranded oligonucleotides.

The target ferrocene-labeled dideoxynucleotide compound 5-[N-(beta-ferrocenyl-propanoyl)3-amino-propyn-1-yl]-2',3'-dideoxyuridine 5'-triphosphate, Fc-ddUTP, was synthesized and tested with terminal deoxynucleotidyl transferase for enzymatic 3'-redox-active end-labeling of 5'-phosphorylated single-stranded oligodeoxynucleotides. Starting from readily available 5-iodouridine and 3-ferrocenylpropanoic acid, the synthetic strategy elaborated here follows a mild multistep route. Each step involves reliable methods, and all ferrocene intermediates can be easily purified. Enzymatic 3'-ferrocene end-labeling of 5'-phosphorylated oligonucleotides is remarkably efficient, and 3'-ferrocene-labeled oligonucleotides can thus be prepared in sufficient amounts for further use in surface modifications.

Animals↗